US4826755A - Process of photoetching of superficial coatings based on polymeric materials - Google Patents

Process of photoetching of superficial coatings based on polymeric materials Download PDF

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Publication number
US4826755A
US4826755A US07/067,150 US6715087A US4826755A US 4826755 A US4826755 A US 4826755A US 6715087 A US6715087 A US 6715087A US 4826755 A US4826755 A US 4826755A
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United States
Prior art keywords
photoetching
superficial
excimer laser
polymeric materials
coatings based
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Expired - Fee Related
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US07/067,150
Inventor
Fabio Garbassi
Ernesto Occhiello
Vincenzo Malatesta
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Montedison SpA
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Montedison SpA
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Assigned to MONTEDISON S.P.A. reassignment MONTEDISON S.P.A. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GARBASSI, FABIO, MALATESTA, VINCENZO, OCCHIELLO, ERNESTO
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
    • G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/146—Laser beam

Definitions

  • the present invention relates to a process of photoetching of superficial coatings based on polymeric materials.
  • this invention relates to a process of photoetching of films based on poly-p-xylylenes by excimer laser irradiation.
  • Processes for eliminating polymeric coatings from coated surfaces such as, for example, processes based on treatments of a mechanical type (sandblasting, scraping, etc.), thermal type (flame), and chemical type (washings and baths with corrosive liquids), are known in the art.
  • a drawback of those processes is that they find a good application only when the surfaces to be treated are wide and particularly when it is not necessary to work with predetermined degrees of accuracy as required in some applications in the electronic field.
  • the support plates are coated with insulating films, mainly based on poly-p-xylylenes, with the exception of small well defined areas wherein the electronic contacts must be provided.
  • a very widely used system for avoiding the polymeric coating elimination process is that known as "masking".
  • the areas to be uncovered are protected, before the coating phase, by suitable protective means.
  • the protective means are eliminated and the end product is then ready for the intended use.
  • the "masking" system also presents some drawbacks: for example, it is laborious and expensive, and it can contaminate the support, if adhesive substances are used.
  • microareas also less than one square micron and with geometries of the photoetched parts well defined spatially.
  • the process of the present invention may be applied on superficial polymeric coatings of every type, although superficial coatings based on poly-p-xylylenes and its chlorinated derivatives, such as poly-2-chloro-p-xylylenes, are preferred.
  • the thickness of the film to be photoetched is not critical for the present process; however, films of thickness less than 100 micrometers are preferred.
  • any excimer laser apparatus may be used for the photoetching of superficial coatings based on polymeric materials, with the proviso that the emitted beams have a wavelength equal to or lower than 193 nm.
  • the excimer laser apparatus produced by Lambda Physik, Model EMG 102, that emits at wavelengths of 154 nm, 193 nm, 248 nm, 337 nm, 351 nm.
  • the impulse time of the localized excimer laser beams utilized for the photoetching process of the present invention is generally lower than 100 ns and the frequency is from 1 to 100 Hz.
  • the power for each impulse is lower than 100 mW, the peak power being lower than 10 mW.
  • the operating procedures for the process of the present invention are those per se known in the use of laser beam instruments.
  • optical systems that can be used for the process of the present invention are mirrors and beam splitters, with the purpose opf deviating and/or dividing the laser beam into many secondary beams and, optionally, of directing them to different points of the sample, diaphragms for the geometry of the zone to be photoetched, etc.
  • An excimer laser instrument produced by Lambda Physik, Model EMG 102, was used.
  • the laser beam having a wavelength of 193 nm, was emitted with an impulse time of 30 ns, the power for each impulse being equal to 59 mW, the peak power being 5 mW, and the flux 4 J/cm 2 .

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Drying Of Semiconductors (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Process of photoetching of superficial coatings based on polymeric material comprising the irradiation of the coated surface with localized excimer laser beams having wavelengths equal to or lower than 193 nm.

Description

DESCRIPTION OF THE INVENTION
The present invention relates to a process of photoetching of superficial coatings based on polymeric materials.
More particularly, this invention relates to a process of photoetching of films based on poly-p-xylylenes by excimer laser irradiation.
Processes for eliminating polymeric coatings from coated surfaces such as, for example, processes based on treatments of a mechanical type (sandblasting, scraping, etc.), thermal type (flame), and chemical type (washings and baths with corrosive liquids), are known in the art.
A drawback of those processes is that they find a good application only when the surfaces to be treated are wide and particularly when it is not necessary to work with predetermined degrees of accuracy as required in some applications in the electronic field. For example, in the printed circuit field the support plates are coated with insulating films, mainly based on poly-p-xylylenes, with the exception of small well defined areas wherein the electronic contacts must be provided.
A very widely used system for avoiding the polymeric coating elimination process is that known as "masking". According to this system, the areas to be uncovered are protected, before the coating phase, by suitable protective means. When the coating process is ended, the protective means are eliminated and the end product is then ready for the intended use. However, the "masking" system also presents some drawbacks: for example, it is laborious and expensive, and it can contaminate the support, if adhesive substances are used.
As an alternative to the masking system, systems comprising the use of infrared laser beams have been proposed. These systems also present some drawbacks because they allow one to obtain, by the photoetching, uncovered microareas, but with geometries not well defined.
It has now been discovered, according to the present invention, that the above-mentioned drawbacks are eliminated by a process for the photoetching of superficial coatings of polymeric materials comprising the irradiation of the coated surface with localized excimer laser beams having wavelengths equal to or lower than 193 nm. Localized excimer laser beams having wavelengths of 154 nm or 193 nm are preferred.
According to the present invention, it is possible to obtain, on a surface completely coated with a thin layer of polymeric material, microareas also less than one square micron and with geometries of the photoetched parts well defined spatially.
The process of the present invention may be applied on superficial polymeric coatings of every type, although superficial coatings based on poly-p-xylylenes and its chlorinated derivatives, such as poly-2-chloro-p-xylylenes, are preferred.
The thickness of the film to be photoetched is not critical for the present process; however, films of thickness less than 100 micrometers are preferred.
Any excimer laser apparatus may be used for the photoetching of superficial coatings based on polymeric materials, with the proviso that the emitted beams have a wavelength equal to or lower than 193 nm. For example, the excimer laser apparatus produced by Lambda Physik, Model EMG 102, that emits at wavelengths of 154 nm, 193 nm, 248 nm, 337 nm, 351 nm.
The impulse time of the localized excimer laser beams utilized for the photoetching process of the present invention is generally lower than 100 ns and the frequency is from 1 to 100 Hz.
The power for each impulse is lower than 100 mW, the peak power being lower than 10 mW.
The operating procedures for the process of the present invention are those per se known in the use of laser beam instruments.
It is possible to work in a normal atmospheric environment such as in an environment having a controlled atmosphere or under vacuum and positioning the sample in the focal plane of a lens that has the function of concentrating and focusing the laser beam.
Other optical systems that can be used for the process of the present invention are mirrors and beam splitters, with the purpose opf deviating and/or dividing the laser beam into many secondary beams and, optionally, of directing them to different points of the sample, diaphragms for the geometry of the zone to be photoetched, etc.
For a still better understanding of the present invention and of putting it into practice, some illustrative, but not limitative, examples are now given.
EXAMPLE 1
A polymeric film of poly-2-chloro-p-xylylene having a thickness of 6 micrometers, and supported on a glass sheet having a surface of 10 cm2, was subjected to photoetching for removing the coating from an area of 1.5 mm2.
An excimer laser instrument produced by Lambda Physik, Model EMG 102, was used. The laser beam, having a wavelength of 193 nm, was emitted with an impulse time of 10 ns, the power for each impulse was equal to 12 mW, the peak power was 1 mW, the flux, determined as the quantity of irradiated energy for each superficial unit, was 0.8 J/cm2.
The material underwent photoetching at a rate between 0.3 and 0.5 micrometers/impulse.
Through optical and electronic microscopy and X-rays photoemission spectroscopy, the complete elimination of polymeric film from the area under examination resulted, without an substantial alteration of the zones surrounding the photoetched zone.
EXAMPLE 2
A polymeric film of poly-2-chloro-p-xylylene having a thickness of 15 micrometers, and supported on a steel plate having a surface of 10 cm2, was subjected to photoetching for removing the coating from an area of 1.5 mm2.
An excimer laser instrument produced by Lambda Physik, Model EMG 102, was used. The laser beam, having a wavelength of 193 nm, was emitted with an impulse time of 30 ns, the power for each impulse being equal to 59 mW, the peak power being 5 mW, and the flux 4 J/cm2.
The material underwent photoetching at a rate between 0.3 and 0.5 micrometers/impulse.
Through optical and electronic microscopy and X-rays photoemission spectroscopy, the complete elimination of polymeric film from the area under examination, without any substantial alteration of the zones surrounding the photoetched zone, was effected.

Claims (4)

What is claimed is:
1. A process for the photoetching of superficial coatings of a polymeric material constituted by poly-p-xylylene or chlorinated derivatives thereof, said process comprising the irradiation of the coated surface with a localized excimer laser beam having a wavelength equal to or lower than 193 nm.
2. A process for the photoetching according to claim 1, wherein the localized excimer laser beam has a wavelength of 154 to 193 nm.
3. A process for photoetching according to claim 1, wherein the superficial coating is constituted by poly-2-chloro-p-xylylene.
4. A process for photoetching according to claim 2, wherein the superficial coating is constituted by poly-2-chloro-p-xylylene.
US07/067,150 1986-07-03 1987-06-29 Process of photoetching of superficial coatings based on polymeric materials Expired - Fee Related US4826755A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT21019/86A IT1196447B (en) 1986-07-03 1986-07-03 PHOTOABLATION PROCESS OF SURFACE COATINGS BASED ON POLYMERIC MATERIAL
IT21019A/86 1986-07-03

Publications (1)

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US4826755A true US4826755A (en) 1989-05-02

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US07/067,150 Expired - Fee Related US4826755A (en) 1986-07-03 1987-06-29 Process of photoetching of superficial coatings based on polymeric materials

Country Status (7)

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US (1) US4826755A (en)
EP (1) EP0253237B1 (en)
JP (1) JPS63100726A (en)
CA (1) CA1272377A (en)
DE (1) DE3785396D1 (en)
ES (1) ES2040227T3 (en)
IT (1) IT1196447B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5322986A (en) * 1992-04-06 1994-06-21 Eastman Kodak Company Methods for preparing polymer stripe waveguides and polymer stripe waveguides prepared thereby
US5858801A (en) * 1997-03-13 1999-01-12 The United States Of America As Represented By The Secretary Of The Navy Patterning antibodies on a surface
US6235541B1 (en) 1997-03-13 2001-05-22 The United States Of America As Represented By The Secretary Of The Navy Patterning antibodies on a surface

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4414059A (en) * 1982-12-09 1983-11-08 International Business Machines Corporation Far UV patterning of resist materials

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4321763B1 (en) * 1964-12-24 1968-09-18
US3375110A (en) * 1964-12-24 1968-03-26 Union Carbide Corp Photo-masking system using p-xylylene polymers
JPS5992532A (en) * 1982-11-18 1984-05-28 インタ−ナショナル　ビジネス　マシ−ンズ　コ−ポレ−ション Method of producing positive type resist
JPS6196737A (en) * 1984-10-17 1986-05-15 Toshiba Corp Manufacture of semiconductor device

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4414059A (en) * 1982-12-09 1983-11-08 International Business Machines Corporation Far UV patterning of resist materials

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, vol. 103, No. 4, Jul. 29, 1985, Columbus Ohio, USA, Garmonov, V.I. "Preparation and Study of Some Properties of Poly(p-xylxlene) Films", Abstract No. 23236r.
Chemical Abstracts, vol. 103, No. 4, Jul. 29, 1985, Columbus Ohio, USA, Garmonov, V.I. Preparation and Study of Some Properties of Poly(p xylxlene) Films , Abstract No. 23236r. *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5322986A (en) * 1992-04-06 1994-06-21 Eastman Kodak Company Methods for preparing polymer stripe waveguides and polymer stripe waveguides prepared thereby
US5858801A (en) * 1997-03-13 1999-01-12 The United States Of America As Represented By The Secretary Of The Navy Patterning antibodies on a surface
US6235541B1 (en) 1997-03-13 2001-05-22 The United States Of America As Represented By The Secretary Of The Navy Patterning antibodies on a surface

Also Published As

Publication number Publication date
EP0253237A3 (en) 1989-05-31
ES2040227T3 (en) 1993-10-16
CA1272377A (en) 1990-08-07
EP0253237A2 (en) 1988-01-20
IT8621019A1 (en) 1988-01-03
JPS63100726A (en) 1988-05-02
DE3785396D1 (en) 1993-05-19
EP0253237B1 (en) 1993-04-14
IT1196447B (en) 1988-11-16
IT8621019A0 (en) 1986-07-03

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Owner name: MONTEDISON S.P.A., 31, FORO BUONAPARTE, MILAN, ITA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:GARBASSI, FABIO;OCCHIELLO, ERNESTO;MALATESTA, VINCENZO;REEL/FRAME:004744/0861

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Owner name: MONTEDISON S.P.A., ITALY

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